CN111342043B - Starting battery cathode material and preparation method thereof - Google Patents
Starting battery cathode material and preparation method thereof Download PDFInfo
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- CN111342043B CN111342043B CN202010102783.XA CN202010102783A CN111342043B CN 111342043 B CN111342043 B CN 111342043B CN 202010102783 A CN202010102783 A CN 202010102783A CN 111342043 B CN111342043 B CN 111342043B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of battery preparation, and particularly discloses a starting battery cathode material and a preparation method thereof. The starting battery negative electrode material comprises lead powder, dilute sulfuric acid, water, sodium lignosulphonate, carbon black and barium sulfate. The preparation method comprises the following steps: (1) mixing sodium lignosulphonate, carbon black and barium sulfate to obtain a negative electrode package mixture; (2) performing ball milling on the negative electrode bag mixture for 5-60 min to obtain a ball-milled negative electrode bag; (3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material. The starting battery cathode material prepared by the method can fully disperse the raw material lead powder and the components in the ball-milling cathode bag, thereby improving the low-temperature starting capability of the starting battery.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a starting battery cathode material and a preparation method thereof.
Background
The starting battery is a special battery for starting, lighting, ignition (abbreviated as SLI), and power supply of vehicles and the like. A lead-acid battery is one of the commonly used starting batteries, and generally includes a positive electrode, a negative electrode, a separator, and an electrolyte. The negative electrode of the lead-acid battery is a lead plate filled with spongy lead, the negative electrode material of the lead-acid battery generally contains components such as lead powder, sodium lignosulfonate (dispersing agent), barium sulfate (nucleating agent), carbon black (conductive material) and the like, the components, water, sulfuric acid and the like are added into a paste mixer (horizontal low-speed stirring mixer) for neutralization to form a negative electrode material at one time, and then the negative electrode material is coated to form a negative electrode green plate.
The traditional mixing method of the paste mixer has the defects that the components are not uniformly mixed, the compounds such as barium sulfate, lead powder and the like are heavy, the lignin is light, and the carbon black is lighter, the carbon black which is thrown (with small bulk density) cannot be mixed into the mixture by the mixing method, so that agglomeration and uneven distribution are serious, black lines appear as soon as a mould forming scraper scrapes, the nucleating agent barium sulfate of about several microns cannot be dispersed and distributed by lignin which is not well dispersed, the nucleating effect of the barium sulfate cannot be well played, and the lead sulfate is seriously salted. This phenomenon of the negative electrode material has an important influence on the low-temperature starting ability of the negative electrode material in starting the battery; the low-temperature starting capability is an important index for starting battery investigation; therefore, providing a starting battery anode material with excellent low-temperature starting capability is of great significance for improving the performance of the starting battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a starting battery cathode material and a preparation method thereof. The battery cathode material prepared by the invention has excellent low-temperature starting capability.
The technical problem to be solved by the invention is realized by the following technical scheme:
a starting battery negative electrode material comprises lead powder, dilute sulfuric acid, water, sodium lignosulphonate, carbon black and barium sulfate; wherein, taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 8-11% of dilute sulfuric acid, 10-13% of water, 0.1-0.4% of sodium lignosulfonate, 0.1-0.5% of carbon black and 0.5-1.2% of barium sulfate.
Preferably, the starting battery negative electrode material takes the weight of lead powder as a measurement standard, and the weight usage of each component is as follows: 10-11% of dilute sulfuric acid, 11-12% of water, 0.2-0.3% of sodium lignosulfonate, 0.3-0.4% of carbon black and 0.8-1.0% of barium sulfate.
Preferably, the dilute sulfuric acid is dilute sulfuric acid with the concentration of 1.0-2.0 g/mL.
The preparation method of the starting battery negative electrode material comprises the following steps:
(1) mixing sodium lignosulphonate, carbon black and barium sulfate to obtain a negative electrode package mixture;
(2) performing ball milling on the negative electrode bag mixture for 5-60 min to obtain a ball-milled negative electrode bag;
(3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material.
In the preparation process of the starting battery cathode material, the components such as sodium lignosulphonate, carbon black and barium sulfate are taken out and dispersed separately to form a ball-milling cathode bag; and then, the negative electrode package is mixed with lead powder, dilute sulfuric acid and water in the process of mixing the negative electrode of the lead-acid battery with paste, so that the raw material lead powder and the components in the ball-milling negative electrode package can be fully dispersed, and the low-temperature starting capability of the starting battery is improved.
Preferably, the mixing in step (1) is carried out in a mixer; and (3) performing ball milling in a ball mill in the step (2).
Preferably, the grinding medium in the ball mill is selected to have a density of 2.7-9 g/cm3The metal balls and/or metal oxide ceramic balls of (a); the volume filling rate of the grinding medium in the ball mill is 20-60%.
Further preferably, the metal ball is selected from 304 stainless steel balls; the metal oxide ceramic ball is selected from a zirconium dioxide ceramic ball or an aluminum oxide ceramic ball.
Preferably, the grinding media in the ball mill are graded by metal balls and/or metal oxide ceramic balls with three sizes; respectively are metal balls or metal oxide ceramic balls with the diameter of 2-15 mm; metal balls or metal oxide ceramic balls with the diameter of 15-50 mm; metal balls or metal oxide ceramic balls with a diameter of 50-100 mm.
More preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-50: 1-50: 1-50;
more preferably, the weight ratio of the metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to the metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to the metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-5: 1-5: 1-5;
most preferably, the grinding media in the ball mill are graded by selecting metal balls and/or metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 2-15 mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 15-50 mm; alumina ceramic balls with the diameter of 50-100 mm; the weight ratio of the 304 stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 3-5: 1-2: 1.
the inventor further researches and discovers that the ball milling step is crucial in the preparation process, even though the technicians in the field can think that the components such as sodium lignosulphonate, carbon black, barium sulfate and the like are taken out and dispersed separately to form a ball milling negative electrode bag; however, if only the components such as sodium lignosulfonate, carbon black and barium sulfate are mixed by a common mixer, a high-speed mixer, a horizontal coulter mixer and the like, the components in the negative electrode bag are still not well mixed, because the carbon black is too light and has too large difference with the bulk density of the sodium lignosulfonate and the barium sulfate, the components in the negative electrode bag are still layered and agglomerated after being mixed by the mixers, and the carbon black cannot be distributed and dispersed into other two components. In order to ensure that the components in the negative electrode package can be fully dispersed, the inventor finds that the ball-milled negative electrode package with excellent dispersion performance can be obtained only by carrying out ball milling on the components such as sodium lignosulfonate, carbon black, barium sulfate and the like in the negative electrode package through a horizontal coulter mixer and then a ball mill.
After the step is finished, if a person skilled in the art can think that a horizontal coulter mixer is used for mixing the components such as sodium lignosulfonate, carbon black and barium sulfate, but the components are not subjected to ball milling and dispersing by a subsequent ball mill, the uniformity and the consistency of the obtained composition are still not good enough, the nucleating effect of barium sulfate cannot be well exerted, lead sulfate is seriously salinized, the low-temperature starting capability of a starting battery is poor, and even the national standard requirement cannot be met.
The inventor researches to show that: the ball milling conditions such as the material of the inner wall of the ball mill, the material of the grinding balls, the size of the grinding balls, the grading of the large and small grinding balls, the filling rate of the grinding balls and the like play a very crucial role in whether a ball milling cathode bag with excellent dispersion performance can be obtained or not; under the ball milling condition, the ball milling negative electrode package components are not agglomerated and have uniform specific gravity, no wall adhesion and good material fluidity in the grinding process. The improper selection of the ball milling conditions easily causes the components in the ball milling negative electrode bag to be easily agglomerated and uneven in specific gravity, the material flow is easily adhered to the wall in the ball milling process, and the flowability of the material is also poor, so that the problem that a large amount of cleaning work needs to be performed from the material ball milling stage to the packaging stage, time and labor are consumed, the efficiency is low, continuous production cannot be performed, and the operation difficulty in industrial production is increased.
The invention also provides a starting battery negative electrode plate, which is obtained by coating the starting battery negative electrode material.
Detailed Description
The present invention is further explained below with reference to specific examples, but the scope of protection of the present invention is not limited to the specific examples.
Example 1 preparation of starting battery negative electrode Material
The raw material ratio is as follows: taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 11% of dilute sulfuric acid (1.40g/mL), 13% of water, 0.1% of sodium lignosulfonate, 0.1% of carbon black and 0.5% of barium sulfate;
the preparation method comprises the following steps:
(1) mixing sodium lignosulfonate, carbon black and barium sulfate in a horizontal coulter mixer for 30min to obtain a negative electrode bag mixture;
(2) ball-milling the negative electrode pack mixture in a ball mill for 30min to obtain a ball-milled negative electrode pack; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 25 mm; alumina ceramic balls with the diameter of 75 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 4: 2: 1;
(3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material.
Example 2 preparation of starting battery negative electrode Material
The raw material ratio is as follows: taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 8% of dilute sulfuric acid (1.40g/mL), 10% of water, 0.4% of sodium lignosulfonate, 0.5% of carbon black and 1.2% of barium sulfate;
the preparation method comprises the following steps:
(1) mixing sodium lignosulfonate, carbon black and barium sulfate in a horizontal coulter mixer for 30min to obtain a negative electrode bag mixture;
(2) ball-milling the negative electrode bag mixture in a ball mill for 60min to obtain a ball-milled negative electrode bag; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 60 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 5mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 50 mm; alumina ceramic balls with the diameter of 100 mm; the weight ratio of the stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 20: 10: 1;
(3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material.
Comparative example 1 preparation of starting battery negative electrode Material
The raw material ratio is as follows: taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 11% of dilute sulfuric acid (1.40g/mL), 13% of water, 0.1% of sodium lignosulfonate, 0.1% of carbon black and 0.5% of barium sulfate;
the preparation method comprises the following steps:
(1) mixing sodium lignosulfonate, carbon black and barium sulfate in a horizontal coulter mixer for 30min to obtain a negative electrode bag mixture;
(2) mixing the negative electrode bag mixture in a high-speed mixer for 60min to obtain a negative electrode bag;
(3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material.
Comparative example 2 preparation of starting battery negative electrode Material
The raw material ratio is as follows: taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 11% of dilute sulfuric acid (1.40g/mL), 13% of water, 0.1% of sodium lignosulfonate, 0.1% of carbon black and 0.5% of barium sulfate;
the preparation method comprises the following steps:
(1) mixing sodium lignosulfonate, carbon black and barium sulfate in a horizontal coulter mixer for 30min to obtain a negative electrode bag mixture;
(2) ball-milling the negative electrode pack mixture in a ball mill for 30min to obtain a ball-milled negative electrode pack; the inner wall of the ball mill is made of 304 stainless steel; the volume filling rate of the grinding medium in the ball mill is 45 percent; the grinding medium in the ball mill is graded by metal balls and metal oxide ceramic balls with two sizes; 304 stainless steel balls with the diameter of 10mm are respectively arranged; a 304 stainless steel ball with the diameter of 25 mm; the weight ratio of the 10mm 304 stainless steel ball to the 25mm 304 stainless steel ball is 2: 1;
(3) and mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain the starting battery negative electrode material.
Examples of the experiments
Coating the starting battery negative electrode materials prepared in the examples 1 and 2 and the comparative examples 1 and 2 respectively to prepare starting battery negative electrode plates; then the automobile starting battery with 12V60Ah is assembled, the low-temperature starting capability (evaluated by discharge voltage of 10 seconds, 30 seconds and 90 seconds) of the automobile starting battery at-18 ℃ and-29 ℃ is tested according to the standard GB/T5008-2013, and the test results are shown in the table 1.
TABLE 1 test results of low-temperature starting capability of automobile starting battery
Note: the standard requirement is that the low-temperature starting capability at-18 ℃ is more than or equal to 7.5 in U10 s; u30s is more than or equal to 7.2; u90s is more than or equal to 6.0; low-temperature starting capability at minus 29 ℃, and U10s is more than or equal to 7.5; u30s is more than or equal to 7.2; u90s is more than or equal to 6.0.
As shown by the test results of the low-temperature starting capability of the starting battery cathode material prepared in the embodiment 1-3, the low-temperature starting capability at-18 ℃ and-29 ℃ is far higher than the standard requirement; the preparation method is characterized in that in the preparation process of the battery cathode material, the components such as sodium lignosulphonate, humic acid, carbon black and barium sulfate are firstly taken out and dispersed separately to form a ball-milling cathode bag; and then, the negative electrode package is mixed with lead powder, dilute sulfuric acid and water in the process of mixing the negative electrode of the lead-acid battery with paste, so that the raw material lead powder and the components in the ball-milling negative electrode package can be fully dispersed, and the low-temperature starting capability of the starting battery can be greatly improved.
As can be seen from the low-temperature capacity test result of the starting battery cathode material prepared in the comparative example 1, the low-temperature starting capability at-18 ℃ and-29 ℃ does not meet the standard requirement, and the low-temperature starting capability is far smaller than that of the example 1; this shows that, in the preparation process of the battery negative electrode material, the starting battery negative electrode material with excellent low-temperature starting capability cannot be obtained by mixing the components such as sodium lignosulfonate, humic acid, carbon black and barium sulfate according to the conventional method.
As can be seen from the low-temperature capacity test result of the starting battery cathode material prepared in the comparative example 2, the low-temperature starting capability at-18 ℃ and-29 ℃ does not meet the standard requirement, and the low-temperature starting capability is far smaller than that of the example 1; this shows that in the preparation process of the battery cathode material, the ball milling step is very critical, and the starting battery cathode material with excellent low-temperature starting capability can be obtained only under the ball milling condition of the invention.
Claims (6)
1. A starting battery cathode material is characterized by comprising lead powder, dilute sulfuric acid, water, sodium lignosulphonate, carbon black and barium sulfate; wherein, taking the weight of the lead powder as a measurement standard, the weight and the dosage of each component are respectively as follows: 8-11% of dilute sulfuric acid, 10-13% of water, 0.1-0.4% of sodium lignosulfonate, 0.1-0.5% of carbon black and 0.5-1.2% of barium sulfate;
the starting battery negative electrode material is prepared by a method comprising the following steps:
(1) mixing sodium lignosulphonate, carbon black and barium sulfate to obtain a negative electrode package mixture;
(2) performing ball milling on the negative electrode bag mixture for 5-60 min to obtain a ball-milled negative electrode bag;
(3) mixing the ball-milled negative electrode package with lead powder, dilute sulfuric acid and water, and adding the mixture into a paste mixer to neutralize paste to obtain a starting battery negative electrode material;
the mixing in the step (1) is carried out in a mixer; the ball milling in the step (2) is carried out in a ball mill; the grinding medium in the ball mill is selected to have a density of 2.7-9 g/cm3The metal balls and/or metal oxide ceramic balls of (a); the volume filling rate of the grinding medium in the ball mill is 20-60%; the inner wall of the ball mill is made of 304 stainless steel;
grading the grinding media in the ball mill by using metal balls and/or metal oxide ceramic balls with three sizes, wherein the metal balls or metal oxide ceramic balls with the diameters of 2-15 mm, the metal balls or metal oxide ceramic balls with the diameters of 15-50 mm and the metal balls or metal oxide ceramic balls with the diameters of 50-100 mm are respectively used as the grinding media in the ball mill;
the weight ratio of metal balls or metal oxide ceramic balls with the diameter of 2-15 mm to metal balls or metal oxide ceramic balls with the diameter of 15-50 mm to metal balls or metal oxide ceramic balls with the diameter of 50-100 mm is 1-50: 1-50: 1-50;
the metal ball is selected from 304 stainless steel balls; the metal oxide ceramic ball is selected from a zirconium dioxide ceramic ball or an aluminum oxide ceramic ball.
2. The negative electrode material for the starting battery as claimed in claim 1, wherein the weight amounts of the components are, based on the weight of the lead powder: 10-11% of dilute sulfuric acid, 11-12% of water, 0.2-0.3% of sodium lignosulfonate, 0.3-0.4% of carbon black and 0.8-1.0% of barium sulfate.
3. The negative electrode material for the starting battery as claimed in claim 1, wherein the dilute sulfuric acid is dilute sulfuric acid having a concentration of 1.0-2.0 g/mL.
4. The starting battery negative electrode material according to claim 1, wherein the weight ratio of the metal balls or metal oxide ceramic balls with a diameter of 2 to 15mm, the metal balls or metal oxide ceramic balls with a diameter of 15 to 50mm, and the metal balls or metal oxide ceramic balls with a diameter of 50 to 100mm is 1 to 5: 1-5: 1 to 5.
5. The starting battery negative electrode material according to claim 4, wherein the grinding media in the ball mill are graded by using metal balls and/or metal oxide ceramic balls with three sizes; 304 stainless steel balls with the diameter of 2-15 mm are respectively arranged; zirconium dioxide ceramic balls with the diameter of 15-50 mm; alumina ceramic balls with the diameter of 50-100 mm; the weight ratio of the 304 stainless steel balls to the zirconium dioxide ceramic balls to the aluminum oxide ceramic balls is 3-5: 1-2: 1.
6. a starting battery negative pole plate is characterized in that the starting battery negative pole plate is obtained by coating the starting battery negative pole material of claim 1 or 2.
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